Document rxZpdpJVM7934g64RpzOpRJka

ot ARR2G -- 1383 FINAL REPORT Epidemiology, 220-3W-05 Medical Department 3M Company St. Paul, MN 55144 Date: June 17, 2003 Title: Descriptive Analysis of Serum Fluorochemical Concentrations fromDecatur Employee Participants of the 2002 Medical Surveillarce Program Protocol Number: N/A IRB Approval: N/A Principal Investigator: Co-investigators: Study Director: Geary W. Olsen, D.V.M., Ph.D. Jeffrey H. Mandel, M.D. JeffreHy.Mandel, M.D. 000070 [- ABSTRACT In the Spring 2002, 54 3M Company Decatur (Alabama) employees voluntarily `participated in the fluorochemical medical surveillance program. As partofthis program, a blood sample was collected from each participating employee for determination of five serum fluorochemicak. These fluorochemicals were: perfluorooctanesulfonate(PFOS); N-ethyl perfluorooctanesulfonamidoacetate (PFOSAA); N-methyl `perfluorooctanesulfonamidoacetate (M570); perfluorooctanoate (PFOA); and perfluorohexanesulfonate (PFHS). The serum PFOS concentrations ranged from 0.082 to 4.2580 ppm withanarithmetic meanof 1.621 ppm (95% CI 1.283 - 1.958) anda geometric meanof 1.008 ppm (95% CI 0.733 - 1.388). Noneofthe employees tested had `serum concentrations that exceeded the Biologic Limit Value of ppm for PFOA [range 0.025 -4.810 ppm; arithmetic mean = 1.497ppm (95% CI 1.084-1.910); geometric mean = 0.713 ppm (95% C1 0.483-1.055)). Comparisonofthe employees' 2002 serum fluorochemical concentrations with the most recent previous measurements suggestead declineinconcentrations for PFOA, PFHS, PFOSAAand M570. A decline in serum PFOS concentrations was not observed. Cautious interpretation is warrantedofany trendin serum concentrations because neither potential workplace exposure information oractual timesince lasttestwasincorporatedin the analyses. 000071 | Paes INTRODUCTION In the Spring 2002, the fluorochemical medical surveillance program was offered to employees atthe 3M Company Decatur (Alabama) chemical manufacturing plant. Results have been reported elsewhere for previous fluorochemical medical surveillance programs at theDecaturmanufacturing plant (Olsen et al. 1999; 2001a; 2003a), as well as the 3M Antwerp (Belgium) fluorochemical manufacturing plant (Olsen et al, 1999; 2001b; 20033)andthe 3M Cottage Grove (Minnesota) fluorochemical manufacturing plant(Gillilandand Mandel 1996; Olsen et al. 1998; 2000; 2003b). There were fewer participants in the 2002 Decatur fluorochemical medical surveillance program than in previous examination years (1994, 1997, 2000) a this manufacturing site. This was likelyduetothefactthatthe 2002fluorochemicalmedicalprogramwasofferedafterthe. company's announcement to cease productionofperfluorooctanesulfonyl fluoride (POSF)-related materials. This resulted in fewer production employees at the Decatur `manufacturing site compared to previous years. The purposeofthis study is to report the serum fluorochemical concentrations that were measured in 2002andcompare the participants results with their most recent previous serum concentrations. METHODS The fluorochemical medical surveillance program isofferedto employees at the Decaturmanufacturing site on a periodic basis. Participation is voluntary. Aspartofthe 2002 program, a blood sample was collected from each participating employee for determination of five serum fluorochemicals. These fluorochemicals were: `perfluorooctanesulfonate (PFOS, CsF17S0y) ; N-ethyl 000072 | Pues perfluorooctanesulfonamidoacetate (PFOSAA, CsFirSO:N(CH;CHy)CH,COO); Nmethyl perfluorooctanesulfonamidoacetate (M570, CsF17SO:N(CHs)CH:COO); `perfluorooctanoate (PFOA, C7F1sCO0);andperfluorohexanesulfonate (PHS, CeF13505). The five fluorochemicals were determined by high performance liquid chromatography electrospray tandem mass spectrometry methods (Hansen et al. 2001), Analyses were conducted at Tandem Labs (Salt Lake City, UT) using validated methods that have been detailed elsewhere (Tandem Labs 1999; 20012; 20018). Fluorochemical concentrations were measured in pg/mL and reported as partspermillion (ppm). RESULTS A total of 54 Decatur employees (41 males, 13 females) voluntarily participated in the 2002 fluorochemical medical surveillance program. Measuresofcentral tendency forthe five fluorochemicals are reported in Table 1. Theserum PFOS concentrations ranged from 0.082 to 4.2580 ppm (Table 1) with a mean (arithmoeft1i.6c2)1 ppm (95% CL1.283 - 1.958). Becausetheconcentrations were skewed (i.e. log normal distribution), a geometric meanwasalso calculated for PFOS (1.008 ppm, 95% C1 0.733 - 1.388). Presented in Table 2areresults for the 30 Decatur employees who participated in `both the2000and 2002 fluorochemical medical surveillance programs. Thearithmetic mean differences are based on subtracting the employees' 2000 serum fluorochemical `concentrations from their respective 2002 serum fluorochemical concentrations, There was no statistically significa(npt < .05)meandifference between serum PFOS 000073 Pages concentrationsforthese 30 employees. Ontheotherhand, the mean serum fluorochemical concentrations significantly (p < 05) decreased for PFOA, PFHS, PFOSAA and M570 inthistwo year interval (Table 2). Figures 1 through 5 provide a paired comparisonofthe 30 employees' 2000 and 2002 serum fluorochemical concentrations. Itshouldbe noted that employees labeled #14 and #18 (see x axis) in Figure 1 are the same as employees #4and #16 in Figure 2, respectively. Becauseofthe long serum elimination half-life ofPFOS and PFOA (Burrsetal.2002), we suspect that the 2000 serum concentrationsofthese two employees might have been in error (biased upwards). Presented in Table 3arethe mean differences in serum PFOS and PFOA concentrations for 44 employee participantsofthe 2002 fluorochemical medical surveillance programinrelation to theirmostrecent previous serum fluorochemical measurements (i.e., prior to the 2002 fluorochemical medical surveillance program). The `previously most recent measurementsforthese 44 employees ranged between blood samples collected between 1997 and 2001. Mean serum PFOS concentrations did not decrease for these 44 employees whereas mean serum PFOA concentrations significantly (p<.05) decreased. Data are not presented for PFHS, PFOSAA and M570 because they. were not measured in the 1997 fluorochemical surveillance program which was the most recent previous measurement for some employees. Presented in Table 4arethe mean differences in serum PFOS and PFOA concentrations for the 11 employee participants in the 2002 fluorochemical medical surveillance program who also participated in the PFOA Biologic Limit Value (BLV) `program in 2001 (after completionofthe 2000 fluorochemical medical surveillance 000074 - program). Thepurposeforthe PFOA BLV program is explained, in detail, elsewhere (3M Company 2001). Basically, 3M established the BLV (5 ppm serum PFOA) to represent the best estimate ofa level of a chemical substance or its metabolite in a biologicalfluidthatif present, evenon achronic basis, would not be expectedtoposeo,r comelate with, a significant risk of adverse health effects to the worker(s). By `establishing this BLV at 5 ppm for PFOA, the exposure guideline committee at 3M did not intend to imply that serum levelsof PFOAgreaterthan the BLV immediately impose a significant risk of adverse health effects. However, ifan employee's serum PFOA level either meetsorexceeds the BLV, it should beunderstoodthat corrective actions(which `may include temporary removal from the immediate work area) `may need to be applied, on a case-by-case basis, at the directionof 3M Corporate Occupational Medicine. The PFOA BLV programwasdirected at those workers engaged in the production of PFOA `which,inDecatur, occurred in 1999 and continued into 2001. Noon f te he 11 employees whowere tested in 2001underthedirectionoftheBLV programhadserum PFOA `concentrations that exceeded the BLV (5 ppm) in either 2001or2002 (Table 4). There `was no statistically significant decrease in serum PFOA concentrations among the 11 employees tested in the initial BLV analysis for Decatur in 2001 in relation to serum PFOA concentrations reported in their 2002 fluorochemical medical surveillance examinations (Table 4). Noneofthe remaining 43 participating employeesexceededthe BLV for PFOA in 2002 (Table 1). 00007s Pe? DISCUSSION `The employee participantsofthe 2002 Decatur fluorochemical medical surveillance program had a distribution ofserum PFOS concentrations comparable to the results obtained from prior serum fluorochemical assessments. These previously collected data were obtained from fluorochemical surveillance programs conducted at Decatuirn 1994,1997 or 2000 (Olsenetal. 1999, 2001, 200or3wi2th)a random sample: ofproduction employees in 1998 (Oben et al. 2003c). Likewise, the distributions of serum PFOA, PFHS, PFOSAA and M570 concentrations were similar o prior assessments (Olsen et al. 2003a; 2003; 2003). Analysisofthe 54 employees' 2002 results suggests, overall, there has been a modest decline in the serum concentrations of PFOA, PFHS, PFOSAA and MS70sincethe 2000 fluorochemical medical surveillance program. The mean serum PFOS concentration didnotdecline in this two year time period. Because potential exposurteo POSF-related materials occurred during 2000 and 2001, it is not possible to determine whether the decline in PFOA, PFHS, PFOSAA and MST0 is the result of serum elimination, reduced opportunityforpotential workplace exposure or both. On theotherhand, serum PFOS concentrations did not decrease. This observation may be a functionofpoor serum elimination (Burris et al 2002) and/or `opportunityforpotential workplace exposure to POSF-related materials through 2001 An ongoing study is examining the serum half-lifeofelimination for PFOS, PFOA and PFHS among 27 retirees followed for $ years at the Decatur and Cottage Grove `manufacturing sits. Results from this investigation should be available in 2004, `Presently,theestimatedserumhalf-livesofeliminationforPFOS and PFOAare 8.7 i | Pues years (SD =6.1)and 4.4 years (SD = 3.5), respectively (Burrisetal.2002). These estimates, however, are based on only 9ofthese retirees followed for 18 months. There are several limitations totheanalyses presented in this report. The results arise from a small subsetofemployees who voluntarily participated in the 2002 Decatur fluorochemical medical surveillance program. The number ofemployees in the 2002 fluorochemical medical surveillance program is only 20 percentofthose who participated in the 2000 fluorochemical medical surveillance program (n = 263). Attrition of employees du to production cessation ofPOSF-related materials occurred between 2000 and2002. Unlike2000,noemployeeinterviewdatawerecollectedin 2002toprovidean estimateofexposure to POSF-related production areasforthese workers. Therefore, it `was not possibletoassociate serum fluorochemical concentrations to potential workplace exposuresinthe 2000-2002timeperiod. Actualtime wasnottakenintoaccountinthe comparisonofthe most recent prior test results compared to the 2002 serum fluorochemical measurements. Knowledgeregarding the serum eliminationhalflieof thesefluorochemicalsremains sparse. More precise estimatesoftheserumelimination halflives ofPFOS, PFOA and PFHS are forthcoming from a separate study designed to `analyzethehalflivesfrom 27retireesofthe 3M DecaandtCotutarge Grove `manufacturing sites. Becauseofthese limitations, there needs tobecautious interpretationofanytime trend analysis of the serum fluorochemical concentrations of the 54 Decatur employees who participated in the 2002 fluorochemical medical surveillance program. `We concludethatthe serum fluorochemical concentrationsofthe 54 employees `who voluntarily participated in the 2002 Decatur fluorochemical medical surveillance 000077 Pugs program did not increase to any substantial extentsincethe 2000 fluorochemical medical surveillance program. For a numberofemployees, their serum PFOA, PFHS, BFOSAA `and MS70 serum concentrations appeatorhaevde decreased. Noneofthe employees tested had serum PFOA concentrations that exceeded the PFOA BLVof $ ppm. Cautious interpretation is warrantedofany time trend in serum concentrations because neither potential workplace exposure informationoractual time since last est was not incorporated in the analyses. 000078 2) REFERENCES haBlurfrlisivIeMso,fsLuenvdebrearlgfJlKu,orOolcsheenmiGc,akS.imSpt.soPnauCl,(MMaNn)d:e3lMJ. Co20m0p2a.nyD.eteU.rSm.inEantviiornoofnsmeenrtualm Protection Agency docket AR-226-1086. lGiiplolpirloatnediFnsD,,aMnadncdheollesJtSe.rol1:996.stSudeyroufm opcecrufplautoiroonoacltlaynoeixcpoacsieddamnednh.epaAtmic JeInnzdyMmeesd, 29:560-568. HaqnuasnteintaKtiJv,eCclhaermaectnerLiAz,atEiolnloeffsoorngManEi,cJfolhunosroonchHeOm.ica2l0s01in. biCoolmopgoiucanld-msaptreicciefsi.c,Environ Sci Technol 35:766-770. OeplisdeenmGioWl,ogGiiclliinlvaensdtiFgDa,tiBonuorflreewprMoMdu,ctBiuvrreishoJrMm,onMeasndienlmeJSn, wMiatnhdoeclcuJpHa.ti1o9n9a8l. exApnosure to perfluorooctanoic acid. J Occup Environ Med 40:614-621 OalnsdehnepGaWti,caBnurdrilsipIidM,clMinaincadleclhJeHm,isZtorbyetlesLtRs.in1f9l9u9o.rSoecrheummicpaelrfplruoodruocotcitoanneempslulofyoeneast.e J Occup Environ Med 41:799-806. OhelpsaetnicGeWn,zyBmuersr,ischJoMl,esBtuerrolleawnMdMl,ipoMparontdeeilnsJiHn.a2m0m0o0n.iPulmaspmearfclhuoolreocoycsttaonkoiantien and production workers. Drug Chem Toxicol 23:603-620. 2O0l0s1ean.GDWe,scLroipgtainvePsWu,mSmiamrpyosofnsCeAr,umBufrlruiosroJcMh,emBiucraelllwevMeMls,amLuonndgbeemrpglJoKy,eeM.andel JH. pPaarutlic(iMpaNn)ts:o3fMthCeoymepaarny2.000U.DSe.caEtnuvrirfolunomreoncthaelrnPircoatlemcetidoincaAlgesunrcvyeidlolcankceetpArRo-g2r2a6m.- St. 10302020. OJKl,seMnaGndWe,l SJcHh.mi2c0k0l1ebr.MNDe,sTcireirpteinvseJsMu,mmLoagrayonfPsWe,rBuumrrfilsuoIrMo,chBeumrilcealw lMeMve,lsLaumnodnbegrg employee program. participantsofthe St. Paul (MN):3M year 2000 Company. Antwerp fluorochemical medical U.S. Environmental Protection surveillance Agency docket AR-226-10302020b. `OwlosreknerGsWe,ruBmurpreirsflIuMo,roBocutraknewsuMlMfo,naMtaen(dPeFlOSJH).an2d00p3ear.fluEopriodoecmtiaonlooagteic(aPsFsOeAs)sment of 2c7o0n.centratiaonds medical surveillance examinations. J Occup Environ Med 45:260- | 000079 | Puen Olsen GW, function in ButenhoffJL, Mandel JH. relation to an occupational 2003b. biologic Assessment of limit value for lipid, hepatic and thyroid perfluorooctanoate. St. Paul (MN):3M Company. U.S. Environmental Protection Agency docket AR-226. VOelnskeantGesWw,arLlougPa,nSPcWh,umHpaenrsteJnCK,JM,anSdiemplsJoHn.C2A0,03Bcu.rriAsnJoMc,cuBpuartlieownaMlMex,poVsourraer.ath PP, assessmentof aperfluorooctanesulfony Ind Hyg Assoc J. (in press). fluoride production site. Biomonitoring. Am `PTFaOnSdAe,m LPaFbOs.SA1A9,99N.-AMscsFaOySwEl-idOaHt,ioNn-rEeptoFrOt.SEQ,uaPntOiAta,tiavenddePtFerHmSiniantihounmoafnPsFeOrSu,m by LCiCt/y,MSU/T.M,S.USS.tEundvyiNroo.nmNeWnBtaSl98Pr-o0t8ec2t,ioRneApogretncNoy.dNocWkBeRt9A9R--020265-.12N08W.T Inc.,SaltLake TPFaHnSd,emM5La5b6s.an2d00M15a7.0QiunanhtuitmaatnivseedreutmerbmyinLaCti/oMnSo/fMSP.FOSA,ssPaFyOreSvAa,liPdaFtOiSonArAep,orPtO.AA, USStSu.dyEnNvoi.rNonWmBeSn0t0al-0P4ro0t,ecRteipoonrAtgNeon.cyNWdBocRkOeOt-A1R0-82.26-N1W20T9.Inc. Salt Lake City, UT., `PTFaHnSd,emM5La5b6s.an2d00M15b7.0QiunanhtuitmaatnivseedreutmerbmyinLaCt/ioMnSo/fMPSF.OSA,ssPaFyOrSeAva,liPdFatOiSonAAad,dPenOdAuAm., report. UT, USStuEdnyviNroo.nmNeWnBtaSl00Pr-o0t4ec0t,ioRnepAogretnNcoy.dNocWkBeRt 0AOR--212262-.1N21W0T. Inc, Salt Lake City, f3oMr PCeormflpuaonryo.oct2a0n0o1a.teD[oCcuFm(eCnFt2a)tiCoOn]o.faSnt.OPcacuulpa(tMiNo)na:l3MBiColoomgpiacnayl.LimUi.tS.Value (BLV) Environmental Protection Agency docket AR-226. 000050 Hfisisd i gz og . 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